Polymer and photoresist compositions

ABSTRACT

Disclosed are spirocyclic olefin ploymers, methods of preparing spirocyclic olefin polymers, photoresist compositions including spirocyclic olefin resin binders and methods of forming relief images using such photoresist compositions.

This application is a divisional of U.S. patent application Ser. No.09/511,726, filed on Feb. 24, 2000, now U.S. Pat. No. 6,406,828.

BACKGROUND OF THE INVENTION

This invention relates generally to polymer compositions useful inphotoresist compositions. In particular, this invention relates topolymer compositions including spirocyclic olefin units useful asbinders in photoresist compositions.

Photoresists are photosensitive films used for transfer of images to asubstrate. A coating layer of a photoresist is formed on a substrate andthe photoresist layer is then exposed through a photomask to a source ofactivating radiation. The photomask has areas that are opaque toactivating radiation and other areas that are transparent to activatingradiation. Exposure to activating radiation provides a photoinducedchemical transformation of the photoresist coating to thereby transferthe pattern of the photomask to the photoresist-coated substrate.Following exposure, the photoresist is developed to provide a reliefimage that permits selective processing of a substrate.

A photoresist can be either positive-acting or negative-acting. For mostnegative-acting photoresists, those coating layer portions that areexposed to activating radiation polymerize or crosslink in a reactionbetween a photoactive compound and polymerizable agents of thephotoresist composition. Consequently, the exposed coating portions arerendered less soluble in a developer solution than unexposed portions.For positive-acting photoresists, exposed portions are rendered moresoluble in a developer solution while areas not exposed remaincomparatively less developer soluble. In general, photoresistcompositions include at least a resin binder component and a photoactiveagent.

More recently, chemically-amplified type resists have been increasinglyemployed, particularly for formation of sub-micron images and other highperformance applications. Such photoresists may be negative-acting orpositive-acting and generally include many crosslinking events (in thecase of a negative-acting resist) or deprotection reactions (in the caseof a positive-acting resist) per unit of photogenerated acid. In thecase of positive chemically-amplified resists, certain cationicphotoinitiators have been used to induce cleavage of certain “blocking”groups pendant from a photoresist binder, or cleavage of certain groupscomprising a photoresist binder backbone. See, for example, U.S. Pat.Nos. 5,075,199; 4,968,581; 4,810,613; and 4,491,628 and Canadian PatentApplication 2,001,384. Upon cleavage of the blocking group throughexposure of a coating layer of such a resist, a polar functional groupis formed, e.g. carboxyl or imide, which results in different solubilitycharacteristics in exposed and unexposed areas of the resist coatinglayer. See also R. D. Allen et al. Proceedings of SPIE, 2724:334-343(1996); and P. Trefonas et al. Proceedings of the 11^(th) InternationalConference on Photopolymers (Soc. of Plastics Engineers), pp 44-58 (Oct.6, 1997).

While currently available photoresists are suitable for manyapplications, current resists can also exhibit significant shortcomings,particularly in high performance applications such as formation ofhighly resolved sub-half micron and sub-quarter micron features.

Consequently, interest has increased in photoresists that can bephotoimaged with short wavelength radiation, including exposureradiation of about 250 nm or less, or even about 200 nm or less, such aswavelengths of about 248 nm (provided by a KrF laser) or 193 nm(provided by an ArF exposure tool). Use of such short exposurewavelengths can enable formation of smaller features. Accordingly, aphotoresist that yields well-resolved images upon 248 or 193 nm exposurecould enable formation of extremely small (e.g. sub-quarter micron)features that respond to constant industry demands for smaller dimensioncircuit patterns, e.g. to provide greater circuit density and enhanceddevice performance.

However, many current photoresists are generally designed for imaging atrelatively higher wavelengths, such as I-line (365 nm) and G-line (436nm) exposures, and are generally unsuitable for imaging at shortwavelengths, such as 248 nm and 193 nm. In particular, prior resistsexhibit poor resolution (if any image at all can be developed) uponexposure to these shorter wavelengths. Among other things, currentphotoresists can be highly opaque to extremely short exposurewavelengths, such as 248 nm and 193 nm, thereby resulting in poorlyresolved images. Efforts to enhance transparency for short wavelengthexposure can negatively impact other important performance propertiessuch as substrate adhesion or swelling, which in turn can dramaticallycompromise image resolution.

Cyclic monomer units, particularly those containing functional groups,impart various properties to the resin binder when incorporated into thebackbone of the resin binder. Anhydrides incorporated into the resinbinder backbone help reduce swelling. For example, Barclay et al., TheEffect of Polymer Architecture on the Aqueous Base development ofPhotoresists, Polym. Prepr. (American Chemical Society, Division ofPolymer Chemistry), volume 40(1), pages 438-439, 1999, discloses theincorporation of itaconic anhydride into a photoresist resin binder,such as a (meth)acrylic polymer. However, such anhydrides can undergohydrolysis in the presence of alcohols or other solvents, especiallysolvents that are contaminated with small amounts of water.

Such swelling of resin binders could be even further reduced oreliminated through the use of a binder containing a high proportion ofcyclic monomers in the polymer backbone, particularly cyclic monomerscontaining functional groups. One approach for achieving this is to useonly cyclic monomers in the preparation of the polymer. However, thisapproach suffers from the difficulty in polymerizing such cyclicmonomers, especially when the cyclic monomers contain electronwithdrawing groups, such as anhydrides. In particular,5-norbornene-2,3-dicarboxylic anhydride cannot be easily polymerized.

For example, WO 99/42510 discloses resins useful in photoresistcompositions wherein the resin is composed of norbornenyl monomerscontaining various functional groups. This patent application isdirected to a method for preparing a polycyclic polymer and introducingdifficult to polymerize functionalities into the polymer bypost-polymerization functionalization. Such post polymerizationtreatment avoids the use of monomers containing such difficult topolymerize functionalities as nitrogen containing groups, such asamides, and hydroxyl containing groups, such as alcohols and carboxylicacids. The post polymerization functionalization is achieved by usingcyclic monomers containing protected functionalities, deprotecting thefunctionality to give a free functionality and then reacting the freefunctionality to give a post-functionalized moiety. Drawbacks of thisinvention are that the mass of the polymer resin may change, resultingin shrinkage of the polymer, and a number of extra steps are requiredwhich greatly adds to the time and cost of the preparation.

Polymers containing tricyclic nornornenyl monomers composed of anorbornenyl ring fused to a 5-membered anhydride ring are disclosed inWO 99/42510. However, spirocyclic monomers are not disclosed in thatpatent application.

Japanese Patent Application JP 10 310 640 A, to Maruzen Petrochem Co.Ltd., discloses a variety of spirocyclic olefin monomers including thosecontaining lactone and imide functional groups. Spiropolyimudes are alsodisclosed, however, such polyimides are bound to the polymer backbonethrough the imide nitrogen groups. This patent application does notdisclose spirocyclic monomer units bound to the polymer backbone throughthe olefinic carbons of the spirocyclic olefin monomers.

It is thus desirable to have photoresist compositions that can be imagedat short wavelengths, contain resin binders having reduced swelling andhave better substrate adhesion than known photoresist compositions. Itis further desirable to have photoresist compositions containing resinbinders that have mass persistence and can be prepared with fewreactions or transformations.

SUMMARY OF THE INVENTION

It has been surprisingly found that polymers containing spirocyclicmonomers can be readily obtained without the use of ring-openingpolymerizations. It has also been surprisingly found that resin binderscan be prepared having a high proportion of cyclic monomers in thepolymer backbone, including cyclic monomers having electron withdrawingfunctional groups. It has further been surprisingly found that suchspirocyclic resin binders include, as polymerized units, spirocyclicmonomers bound to the polymer backbone through the monomer olefiniccarbons.

In one aspect, the present invention provides a polymer including aspolymerized units one or more spirocyclic olefin monomers, wherein thespirocyclic olefin monomers are bound to the polymer backbone throughthe olefinic carbons, and optionally one or more ethylenically oracetylenically unsaturated monomers.

In a second aspect, the present invention provides a method ofpolymerizing one or more spirocyclic olefinic monomers to form a polymerincluding as polymerized units one or more spirocyclic olefin monomers,including the step of contacting the one or more spirocyclic olefinicmonomers with one or more catalysts selected from palladium(II)polymerization catalyst, nickel(II) polymerization catalyst and freeradical polymerization catalyst.

In a third aspect, the present invention provides a photoresistcomposition including a resin binder including as polymerized units oneor more spirocyclic olefin monomers, wherein the spirocyclic olefinmonomers are bound to the polymer backbone through the olefinic carbons,optionally one or more ethylenically or acetylenically unsaturatedmonomers and a photoactive component.

In a fourth aspect, the present invention provides a method for forminga photoresist relief image, including the steps of applying a coatinglayer of the photoresist composition described above; exposing thephotoresist coating layer to patterned activating radiation; developingthe exposed photoresist coating layer to provide a photoresist reliefimage.

DETAILED DESCRIPTION OF THE INVENTION

As used throughout this specification, the following abbreviations shallhave the following meanings, unless the context clearly indicatesotherwise: ° C.=degrees Centigrade; g=gram; mol=mole; mol %=percent bymoles; w/w=weight per weight basis; mmol=millimole; ml=milliliter;mm=millimeter; nm=nanometer; Ar=aryl; and sec=second.

The terms “resin” and “polymer” are used interchangeably throughout thisspecification. The term “alkyl” refers to linear, branched and cyclicalkyl. The terms “halogen” and “halo” include fluorine, chlorine,bromine, and iodine. Thus the term “halogenated” refers to fluorinated,chlorinated, brominated, and iodinated. “Polymers” refer to bothhomopolymers and copolymers. The term “(meth)acrylate” refers to bothacrylate and methacrylate. Likewise, the term “(meth)acrylic” refers toboth acrylic and methacrylic.

All amounts are percent by weight and all ratios are by weight, unlessotherwise noted. All numerical ranges are inclusive.

The present invention provides a polymer including as polymerized unitsone or more spirocyclic olefin monomers. The term “spirocyclic” as usedherein has its conventional meaning, that is, any compound containingtwo or more rings wherein two of the rings have one ring carbon incommon. By “spirocyclic olefin” is meant any spirocyclic compound havinga double bond. “Sprirocyclic olefin monomer” refers to any spirocyclicolefin capable of being polymerized.

The polymers of the present invention contain from 1 to 100 percent byweight, based on the total weight of the monomers, of one or morespirocyclic monomers. Thus the polymers of the present invention may behomopolymers or copolymers of spirocyclic olefin monomers. It will beappreciated by those skilled in the art that any ethylenicallyunsaturated monomer, acetylenically unsaturated monomer or mixturesthereof may be copolymerized with the spirocyclic olefin monomers of thepresent invention. Such ethylenically or acetylenically unsaturatedmonomer or mixtures thereof may be present in the polymers of thepresent invention in an amount in the range of 1 to 99 percent byweight, based on the total weight of the monomers.

Any spirocyclic olefin monomer is useful in the polymers of the presentinvention. It is preferred that at least one ring of the spirocyclicolefin monomer is a 5- to 7-membered ring, and more preferably bothspirocyclic rings are 5- to 7-membered rings. Suitable spirocyclicolefin monomers useful in the present invention include those of FormulaI

wherein A=O, S, CH₂, and NR¹; R¹=phenyl, substituted phenyl, benzyl,substituted benzyl, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; G═C(Z′),O, S, and NR²; R²═(C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; E and W areindependently selected from C(Z′), O, NR² and a chemical bond; Z′═O orS; n=0 to 3; m=0 to 2; m′=0 to 2; 1=0 to 5; and p=0 to 5; provided that1+p=3 to 5; provided that when A=O, S or NR¹; n=1; wherein T and L aretaken together and selected from a double bond or a 5 to 8-memberedunsaturated ring.

Suitable spirocyclic monomers of the present invention wherein T and Lare joined to form a 5 to 8-membered unsaturated ring include thosehaving the Formula Ia

wherein A, E, W, G, l, m, n and p are as defined above.

It is preferred that the spirocyclic olefin monomers of the presentinvention have the structure of Formula Ib

wherein A, E, W, G, l, m, n and p are as defined above. More preferably,the spirocyclic olefin monomers have the structure of Formula Ic

wherein A, E, W, G, l, m, n and p are as defined above. It is furtherpreferred that n is 1 or 2. It is still further preferred that A is CH₂.It is also preferred that m is 0 or 1.

By “substituted phenyl” is meant a phenyl ring having one or more of itshydrogens replaced with another substituent group. By “substitutedbenzyl” is meant a benzyl group having one or more of its hydrogensreplaced with another substituent group. Suitable substituent groupsinclude, but are not limited to, cyano, halo, (C₁-C₄)alkoxy,(C₁-C₄)alkyl, amino, (C₁-C₄)alkylamino, (C₁-C₄)dialkylamino,(C₁-C₄)alkylthio, and the like.

The spirocyclic olefin monomers useful in the present invention may beoptionally substituted. By substituted is meant that one or more of thehydrogens on the ring carbons is replaced by one or more substituentgroups. Suitable substituent groups include (C₁-C₁₂)alkyl, phenyl,substituted phenyl, (C₁-C₁₂)alkoxy, (C₇-C₁₀)alkaryl,(C₁-C₈)perhaloalkyl, and halogen. Preferred substituents are(C₁-C₁₂)alkyl, more preferably (C₁-C₄)alkyl, and most preferably(C₁-C₂)alkyl.

Preferred spirocyclic olefin monomers are those containing electronwithdrawing groups within at least one of the spirocyclic rings. As usedherein, spirocyclic olefin monomers containing electron withdrawinggroups are intended to include compounds having groups such as carbonyl,thiocarbonyl, oxa, mercapto, amino, substituted amino, amido, and thelike as ring atoms. Suitable electron withdrawing groups include, butare not limited to anhydrides, thioanhydrides, lactones, thiolactones,imides, thioimides, lactams and thiolactams. It is preferred that theelectron withdrawing groups are anhydrides, lactones, imides andlactams, and more preferably anhydrides and lactones. It is furtherpreferred that such electron withdrawing groups are alpha to thespirocarbon.

Suitable spirocyclic olefin monomers include, but are not limited to,spirocyclic norbornenyl monomers, spirocyclic cyclohexene monomers,spirocyclic cyclopentene monomers and mixtures thereof. Suitablespirocyclic norbornenyl monomers include those having a 5-memberedspirocycle, such as those of Formulae II and III

wherein Z═CH₂, C(O), C(S), O or S; X and Y are independently selectedfrom CH₂, C(O), C(S), O or NR²; and R²═(C₁-C₈)alkyl and substituted(C₁-C₈)alkyl; provided that at least one of X, Y and Z is selected fromC(O) or C(S); and wherein the spirocyclic monomer is optionallysubstituted.

Preferred spirocyclic norbornenyl olefin monomers of Formulae II and IIIare those wherein Z is C(O), and more preferably wherein Z is C(O) and Xis oxygen. Spirocyclic norbornenyl olefin monomers having a carbonyl orthiocarbonyl in the exo position are preferred in certainpolymerizations as polymerizations of such exo monomers are believed tobe faster than that of the corresponding endo monomers. Thus, forexample, spirocyclic norbornenyl olefin monomers of Formula II arepreferred when Z is C(O) or C(S).

The spirocyclic olefinic monomers useful in the present invention aregenerally known in the literature. For example, Griffini, Heterocycles,volume 16, number 5, pages 775-788, 1981, discloses various spirocyclicolefinic imides, herein incorporated by reference to the extent thisarticle teaches the preparation of such compounds.

In general, the spirocyclic olefin monomers of the present invention maybe prepared by a Diels-Alder reaction of a cyclic hydrocarbon containingan exo double bond with butadiene, a substituted butadiene, acyclodiene, such as cyclopentadiene or 1,3-cyclohexadiene, or asubstituted cyclodiene. Such reaction is illustrated in the followingReaction Scheme.

The ethylenically or acetylenically unsaturated monomers that may beused in the present invention are any that will copolymerize with thespirocyclic olefinic monomers of the present invention. It will beappreciated by those skilled in the art that one or more ethylenicallyor acetylenically unsaturated monomers may be copolymerized with thespirocyclic olefinic monomers of the present invention. The total amountof the ethylenically and acetylenically monomers useful in the polymerof the present invention is from 1 to 99 percent by weight, based on thetotal weight of the monomers, preferably from 10 to 95 percent byweight, more preferably from 20 to 90 percent by weight, and even morepreferably from 60 to 90 percent by weight.

Suitable ethylenically or acetylenically unsaturated monomers include,but are not limited to: (meth)acrylic acid, (meth)acrylamides, alkyl(meth)acrylates, alkenyl (meth)acrylates, aromatic (meth)acrylates,vinyl aromatic monomers, nitrogen-containing compounds and theirthio-analogs, substituted ethylene monomers, cyclic olefins, substitutedcyclic olefins, and the like.

Typically, the alkyl (meth)acrylates useful in the present invention are(C₁-C₂₄)alkyl (meth)acrylates. Suitable alkyl (meth)acrylates include,but are not limited to, “low cut” alkyl (meth)acrylates, “mid cut” alkyl(meth)acrylates and “high cut” alkyl (meth)acrylates.

“Low cut” alkyl (meth)acrylates are typically those where the alkylgroup contains from 1 to 6 carbon atoms. Suitable low cut alkyl(meth)acrylates include, but are not limited to: methyl methacrylate(“MMA”), methyl acrylate, ethyl acrylate, propyl methacrylate, butylmethacrylate (“BMA”), butyl acrylate (“BA”), isobutyl methacrylate(“IBMA”), hexyl methacrylate, cyclohexyl methacrylate, cyclohexylacrylate and mixtures thereof.

“Mid cut” alkyl (meth)acrylates are typically those where the alkylgroup contains from 7 to 15 carbon atoms. Suitable mid cut alkyl(meth)acrylates include, but are not limited to: 2-ethylhexyl acrylate(“EHA”), 2-ethylhexyl methacrylate, octyl methacrylate, decylmethacrylate, isodecyl methacrylate (“IDMA”, based on branched(C₁₀)alkyl isomer mixture), undecyl methacrylate, dodecyl methacrylate(also known as lauryl methacrylate), tridecyl methacrylate, tetradecylmethacrylate (also known as myristyl methacrylate), pentadecylmethacrylate and mixtures thereof. Particularly useful mixtures includedodecyl-pentadecyl methacrylate (“DPMA”), a mixture of linear andbranched isomers of dodecyl, tridecyl, tetradecyl and pentadecylmethacrylates; and lauryl-myristyl methacrylate (“LMA”).

“High cut” alkyl (meth)acrylates are typically those where the alkylgroup contains from 16 to 24 carbon atoms. Suitable high cut alkyl(meth)acrylates include, but are not limited to: hexadecyl methacrylate,heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate,cosyl methacrylate, eicosyl methacrylate and mixtures thereof.Particularly useful mixtures of high cut alkyl (meth)acrylates include,but are not limited to: cetyl-eicosyl methacrylate (“CEMA”), which is amixture of hexadecyl, octadecyl, cosyl and eicosyl methacrylate; andcetyl-stearyl methacrylate (“SMA”), which is a mixture of hexadecyl andoctadecyl methacrylate.

The mid-cut and high-cut alkyl (meth)acrylate monomers described aboveare generally prepared by standard esterification procedures usingtechnical grades of long chain aliphatic alcohols, and thesecommercially available alcohols are mixtures of alcohols of varyingchain lengths containing between 10 and 15 or 16 and 20 carbon atoms inthe alkyl group. Examples of these alcohols are the various Zieglercatalyzed ALFOL alcohols from Vista Chemical company, i.e., ALFOL 1618and ALFOL 1620, Ziegler catalyzed various NEODOL alcohols from ShellChemical Company, i.e. NEODOL 25L, and naturally derived alcohols suchas Proctor & Gamble's TA-1618 and CO-1270. Consequently, for thepurposes of this invention, alkyl (meth)acrylate is intended to includenot only the individual alkyl (meth)acrylate product named, but also toinclude mixtures of the alkyl (meth)acrylates with a predominant amountof the particular alkyl (meth)acrylate named.

The alkyl (meth)acrylate monomers useful in the present invention may bea single monomer or a mixture having different numbers of carbon atomsin the alkyl portion. Also, the (meth)acrylamide and alkyl(meth)acrylate monomers useful in the present invention may optionallybe substituted. Suitable optionally substituted (meth)acrylamide andalkyl (meth)acrylate monomers include, but are not limited to: hydroxy(C₂-C₆)alkyl (meth)acrylates, dialkylamino(C₂-C₆)-alkyl (meth)acrylates,dialkylamino(C₂-C₆)alkyl (meth)acrylamides.

Particularly useful substituted alkyl (meth)acrylate monomers are thosewith one or more hydroxyl groups in the alkyl radical, especially thosewhere the hydroxyl group is found at the β-position (2-position) in thealkyl radical. Hydroxyalkyl (meth)acrylate monomers in which thesubstituted alkyl group is a (C₂-C₆)alkyl, branched or unbranched, arepreferred. Suitable hydroxyalkyl (meth)acrylate monomers include, butare not limited to: 2-hydroxyethyl methacrylate (“HEMA”), 2-hydroxyethylacrylate (“HEA”), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethylmethacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethylacrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate andmixtures thereof. The preferred hydroxyalkyl (meth)acrylate monomers areHEMA, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylateand mixtures thereof. A mixture of the latter two monomers is commonlyreferred to as “hydroxypropyl methacrylate” or HPMA.

Other substituted (meth)acrylate and (meth)acrylamide monomers useful inthe present invention are those with a dialkylamino group ordialkylaminoalkyl group in the alkyl radical. Examples of suchsubstituted (meth)acrylates and (meth)acrylamides include, but are notlimited to: dimethylaminoethyl methacrylate, dimethylaminoethylacrylate, N,N-dimethylaminoethyl methacrylamide,N,N-dimethyl-aminopropyl methacrylamide, N,N-dimethylaminobutylmethacrylamide, N,N-di-ethylaminoethyl methacrylamide,N,N-diethylaminopropyl methacrylamide, N,N-diethylaminobutylmethacrylamide, N-(1,1-dimethyl-3-oxobutyl) acrylamide,N-(1,3-diphenyl-1-ethyl-3-oxobutyl) acrylamide,N-(1-methyl-1-phenyl-3-oxobutyl) methacrylamide, and 2-hydroxyethylacrylamide, N-methacrylamide of aminoethyl ethylene urea, N-methacryloxyethyl morpholine, N-maleimide of dimethylaminopropylamine and mixturesthereof.

Other substituted (meth)acrylate monomers useful in the presentinvention are silicon-containing monomers such as γ-propyltri(C₁-C₆)alkoxysilyl (meth)acrylate, γ-propyl tri(C₁-C₆)alkylsilyl(meth)acrylate, γ-propyl di(C₁-C₆)alkoxy(C₁-C₆)alkylsilyl(meth)acrylate, γ-propyl di(C₁-C₆)alkyl(C₁-C₆)alkoxysilyl(meth)acrylate, vinyl tri(C₁-C₆)alkoxysilyl (meth)acrylate, vinyldi(C₁-C₆)alkoxy(C₁-C₆)alkylsilyl (meth)acrylate, vinyl(C₁-C₆)alkoxydi(C₁-C₆)alkylsilyl (meth)acrylate, vinyltri(C₁-C₆)alkylsilyl (meth)acrylate, and mixtures thereof.

The vinyl aromatic monomers useful as unsaturated monomers in thepresent invention include, but are not limited to: styrene (“STY”),α-methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene,vinylnaphthalene, vinylxylenes, and mixtures thereof. The vinylaromaticmonomers also include their corresponding substituted counterparts, suchas halogenated derivatives, i.e., containing one or more halogen groups,such as fluorine, chlorine or bromine; and nitro, cyano, (C₁-C₁₀)alkoxy,halo(C₁-C₁₀)alkyl, carb(C₁-C₁₀)alkoxy, carboxy, amino,(C₁-C₁₀)alkylamino derivatives and the like.

The nitrogen-containing compounds and their thio-analogs useful asunsaturated monomers in the present invention include, but are notlimited to: vinylpyridines such as 2-vinylpyridine or 4-vinylpyridine;lower alkyl (C₁-C₈) substituted N-vinyl pyridines such as2-methyl-5-vinyl-pyridine, 2-ethyl-5-vinylpyridine,3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinyl-pyridine, and2-methyl-3-ethyl-5-vinylpyridine; methyl-substituted quinolines andisoquinolines; N-vinylcaprolactam; N-vinylbutyrolactam;N-vinylpyrrolidone; vinyl imidazole; N-vinyl carbazole;N-vinyl-succinimide; (meth)acrylonitrile; o-, m-, or p-aminostyrene;maleimide; N-vinyl-oxazolidone; N,N-dimethyl aminoethyl-vinyl-ether;ethyl-2-cyano acrylate; vinyl acetonitrile; N-vinylphthalimide;N-vinyl-pyrrolidones such as N-vinyl-thio-pyrrolidone, 3methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone,5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone,3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone,4,5-dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone,3,3,5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone,5-methyl-5-ethyl-1-vinyl-pyrrolidone and3,4,5-trimethyl-1-vinyl-pyrrolidone; vinyl pyrroles; vinyl anilines; andvinyl piperidines.

The substituted ethylene monomers useful as unsaturated monomers is inthe present invention include, but are not limited to: vinyl acetate,vinyl formamide, vinyl chloride, vinyl fluoride, vinyl bromide,vinylidene chloride, vinylidene fluoride, vinylidene bromide anditaconic anhydride.

Suitable cyclic olefin monomers useful in the present invention are(C₅-C₁₀)cyclic olefins, such as cyclopentene, cyclopentadiene,dicylopentene, cyclohexene, cyclohexadiene, cycloheptene,cycloheptadiene, cyclooctene, cyclooctadiene, norbornene, maleicanhydride and the like. Suitable substituted cyclic olefin monomersinclude, but are not limited to, cyclic olefins having one or moresubstituent groups selected from hydroxy, aryloxy, halo, (C₁-C₁₂)alkyl,(C₁-C₁₂)haloalkyl, (C₁-C₁₂)hydroxyalkyl, (C₁-C₁₂)halohydroxyalkyl suchas (CH₂)_(n′)C(CF₃)₂OH where n′=0 to 4, (C₁-C₁₂)alkoxy, thio, amino,(C₁-C₆)alkylamino, (C₁-C₆)dialkylamino, (C₁-C₁₂)alkylthio,carbo(C₁-C₂₀)alkoxy, carbo(C₁-C₂₀)haloalkoxy, (C₁-C₁₂)acyl,(C₁-C₆)alkylcarbonyl(C₁-C₆)alkyl, and the like. Particularly suitablesubstituted cyclic olefins include maleic anhydride and cyclic olefinscontaining one or more of hydroxy, aryloxy, (C₁-C₁₂)alkyl,(C₁-C₁₂)haloalkyl, (C₁-C₁₂)hydroxyalkyl, (C₁-C₁₂)halohydroxyalkyl,carbo(C₁-C₂₀)alkoxy, and carbo(C₁-C₂₀)haloalkoxy. It will be appreciatedby those skilled in the art that the alkyl and alkoxy substituents maybe optionally substituted, such as with halogen, hydroxyl, cyano,(C₁-C₆)alkoxyl, mercapto, (C₁-C₆)alkylthio, amino, acid labile leavinggroup and the like.

Suitable carbo(C₁-C₂₀)alkoxy substituents include, but are not limitedto, those of the formula C(O)O-LG, wherein LG is a leaving group having4 or more carbon atoms with at least one quaternary carbon atom bondeddirectly to the carboxyl group. Suitable leaving groups include, but arenot limited to, isobutyl, 2,3-dimethylbutyl, 2,3,4-trimethylpentyl andalicyclic leaving groups. Suitable alicyclic leaving groups includeadamantyl, methyladamantyl, ethyladamantyl, methylnorbornyl,ethylnorbornyl, ethyltrimethylnorbornyl, and the like. Particularlyuseful alicyclic leaving groups are those of Formulae IVa-IVd.

Other particularly useful cyclic olefin monomer substituents include,but are not limited to, Ar—O—LG and (CH₂)_(n′)C(CF₃)₂O-LG where n′=0 to4, wherein LG is as described above. It is preferred that the aryl groupis phenyl.

Suitable ethylenically unsaturated cyclic olefins having one or morehydroxy groups include, but are not limited to, norbornenyl alcohols ofFormula (V)

wherein R¹, R² and R³ are independently hydrogen and (C₁-C₈)alkyl andwherein R¹ and R³ may be joined to form a 5- to 7-member fused ring. Itis preferred that R¹ and R³ are independently selected from hydrogen or(C₁-C₈)alkyl, R²=cyclohexyl or cyclopentyl, and R² and R³ may be joinedto form a 5- to 7-member fused ring. It is further preferred that R¹ ishydrogen or methyl. Particularly useful norbornenyl alcohols are thoseof the Formulae Va-Vc.

The spirocyclic polymers of the present invention may be prepared by avariety of methods, such as free-radical polymerization and metalcatalyzed polymerization. Any catalyst is suitable for use in thepresent invention as long as it catalyzes the polymerization of thedouble bond of the spirocyclic olefinic monomers without substantiallyopening the rings of the spirocyclic monomer. Metal catalyzedpolymerizations are preferred. Suitable free-radical polymerizationcatalysts include, but are not limited to: hydrogen peroxide, tert-butylhydroperoxide, sodium persulfate, potassium persulfate, lithiumpersulfate; and the like. Such free-radical polymerization conditionswill be clear to those skilled in the art.

It will be appreciated by those skilled in the art that more than onemetal catalyst may be used in the polymerizations of the presentinvention. Suitable metal polymerization catalysts include, but are notlimited to, palladium(II) catalysts, such as palladium dihalide,nonionic palladium(II)-halide complexes, (Pd(RCN)₄)(BF₄)₂, where R is(C₁-C₄)alkyl, palladium(II)-alkyl complexes, and (η³-allyl)palladium(II)compounds with weakly coordinating counterions. Preferred palladium(II)catalysts are (Pd(RCN)₄)(BF₄)₂, where R is (C₁-C₄)alkyl,(η³-allyl)palladium(II) compounds with weakly coordinating counterions,and mixtures thereof. Particularly useful palladium(II) catalystsinclude, but are not limited to: (Pd(CH₃CN)₄)(BF₄)₂,(Pd(C₂H₅CN)₄)(BF₄)₂, (η³-allyl)Pd(BF₄), ((η³-allyl)PdCl)₂,(η³-allyl)Pd(SbF₆), and mixtures of (η³-allyl)Pd(BF4) and(η³-allyl)Pd(SbF₆). Such catalysts are generally known, see, forexample, Mathew et al., (η³-Allyl)palladium(II) and Palladium(II)Nitrile Catalysts for the Addition Polymerization of NorborneneDerivatives with Functional Groups, Macromolecules, vol. 29, pages2755-2763, 1996, herein incorporated by reference to the extent itteaches the preparation and use of such catalysts.

Other suitable metal polymerization catalysts include nickel(II)catalysts having as ligands at least one of salicylaldimine orsubstituted salicylaldimine and at least one of acetonitrile or aphosphine, such as triphenylphosphine. Suitable substitutedsalicylaldimine ligands include those substituted in the ortho positionto the oxygen with a bulky group, such as phenyl, substituted phenyl,anthracene, substituted anthracene, triphenylmethyl, meta-terphenyl andthe like. Suitable catalysts are those disclosed in Younkin et al.,Neutral, Single-Component Nickel (II) Polyolefin Catalysts that TolerateHeteroatoms, Science, vol. 287, pp 460-462, Jan. 21, 2000.

The ratio of monomer to metal catalyst in the polymerization reaction ofthe present invention can range from about 5000:1 to about 25:1,preferably from 1000:1 to 50:1, and more preferably from 100:1 to 50:1.The polymerization reaction using this catalyst can be run in ahydrocarbon solvent, such as cyclohexane, toluene, benzene,nitrobenzene, chlorobenzene, nitromethane, dichloromethane and mixturesthereof. A particularly useful solvent mixture is nitrobenzene anddichlorobenzene in a 4:1 ratio. The polymerization reactions usingpalladium(II) catalysts can be carried out at a temperature in the rangeof from about 0° to about 70° C. It is preferred that the polymerizationreaction is carried out at a temperature of 10° to 50° C., and morepreferably 20° to 40° C. The yields for the polymerizations aretypically in the range of 25 to 100%.

The spirocyclic polymers of the present invention may be used in anyapplication where cyclic polymers may be useful. The spirocyclicpolymers of the present invention are particularly useful in electronicsapplications, such as, but not limited to, photoresist compositions,antireflective coating compositions, soldermasks, dielectrics, and thelike. Spirocyclic polymers of the present invention containing aspolymerized units one or more spirocyclic olefin monomers containing oneor more electron withdrawing groups are particularly suitable for use asresin binders in photoresist compositions. When used in photoresistcompositions, such spirocyclic polymers of the present invention showreduced swelling and improved adhesion over known photoresistcompositions.

Particularly suitable spirocyclic polymers of the present invention foruse in photoresist compositions include those of Formula VIa and VIb

wherein Z═CH₂, C(O), C(S), O or S; X and Y are independently selectedfrom CH₂, C(O), C(S), O or NR²; R²═(C₁-C₈)alkyl and substituted(C₁-C₈)alkyl; R³═C(O)O(CH₂)_(q)OH, H and C(O)OR⁴; R⁴═(C₁-C₂₄)alkyl andH; J═C(O)O—, Ar—O— and (CH₂)_(n′)C(CF₃)₂—O—; LG is leaving group having4 or more carbon atoms with at least one quaternary carbon atom bondeddirectly to the carboxyl group; q is an integer from 0 to 20; n′=0 to 4;r is 10 to 60 percent by weight of the monomer unit, based on the totalweight of the monomers; r′ is 10 to 80 percent by weight of the monomerunit, based on the total weight of the monomers; t is 10 to 90 percentby weight of the monomer unit, based on the total weight of themonomers; t′ is 20 to 90 percent by weight of the monomer unit, based onthe total weight of the monomers; and p is 0 to 80 percent by weight ofthe monomer unit, based on the total weight of the monomers. It ispreferred that the t+p is in the range of 20 to 90 percent by weightbased on the total weight of the monomers, and more preferably in therange of 60 to 90 percent by weight.

Other particularly suitable spirocyclic polymers of the presentinvention, particularly for use in photoresist systems, include aspolymerized units one or more spirocyclic olefin monomers of the presentinvention, maleic anhydride, one or more cyclic olefin monomers havingas a substituent a leaving group as described herein and optionally oneor more other monomers. Suitable optional monomers in these polymersinclude, but are not limited to, norbornene, itaconic anhydride,(meth)acrylate esters and the like.

Other particularly suitable spirocyclic polymers of the presentinvention for use in photoresist compositions are those containing aspolymerized units one or more spriocyclic olefin monomers of FormulaeVII and VIII

wherein R⁵═(C₁-C₂₄)alkyl and v is an integer between 1 and 4. It ispreferred that R⁵═(C₁-C₆)alkyl, and more preferably (C₁-C₄)alkyl. Whilenot intending to be bound by theory, it is believed that in certaincases, such as when v is 3 or greater, such spirocyclic olefin monomersmay ring open in the presence of an acid to yield a norbornenyl compoundcontaining as pendant groups both a carboxylic acid and an alkene. Thus,such spirocyclic monomer units, when polymerized into a polymer, mayalso ring open in the presence of an acid. Such ring opening affords acyclic polymer backbone having carboxylic acid functionality and analkenyl group without the loss of any significant mass. Thus, not onlycan an acid functionality can be introduced into a cyclic polymerbackbone with fewer reaction steps than known methods, but the resultingspirocyclic polymers show mass persistence, that is, they do notsignificantly shrink. Spirocyclic polymers containing as polymerizedunits one or more 7-membered or higher-membered spirocyclic olefinmonomers are thus particularly useful in photoresist compositions.

The photoresist compositions of the present invention include one ormore photoactive components, one or more spirocyclic resin binders ofthe present invention, and optionally one or more additives. Thephotoactive components useful in the present invention are typicallyphotoacid or photobase generators, and preferably photoacid generators.

The photoacid generators useful in the present invention are anycompounds which liberate acid upon exposure to light, typically at awavelength of about 320 to 420 nanometers, however other wavelengths maybe suitable. Suitable photoacid generators include halogenatedtriazines, onium salts, sulfonated esters and halogenated sulfonyloxydicarboximides.

Particularly useful halogenated triazines includehalomethyl-s-triazines. Suitable halogenated triazines include forexample,2-[1-(3,4-benzodioxolyl)]-4,6-bis(trichloromethyl)-1,2,5-triazine,2-[1-(2,3-benzodioxolyl)]-4,6-bis(trichloromethyl)-1,3,5-thiazine,2-[1-(3,4-benzodioxolyl)]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[1-(2,3-benzodioxolyl)]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(2-furfylethylidene)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(4-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(3-methylfuryl)ethylidene]-4,6-bis-(trichloromethyl)-1,3,5-triazine,2-[2-(4,5-dimethylfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(5-methoxyfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(4-methoxyfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(3-methoxyfuryl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(4,5-dimethoxy-furyl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(2-furfylethylidene)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(5-methylfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(4-methylfuryl)-ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(3-methylfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(4,5-dimethoxyfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(5-methoxyfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(4-methoxyfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(3-methoxyfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2-[2-(4,5-dimethoxyfuryl)ethylidene]-4,6-bis(tribromomethyl)-1,3,5-triazine,2,4,6-tris-(trichloromethyl)-1,3,5-triazine,2,4,6-tris-(tribromomethyl)-1,3,5-triazine,2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine,2-phenyl-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxyphenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(1-naphthyl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxy-1-naphthyl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-styryl-4,6-bis(trichloromethyl)-1,3,5-triazine,2-styryl-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxystyryl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(3,4,5-trimethoxystyryl)-4,6-bis(tribromomethyl)-1,3,5-triazine,2-(3-chloro-1-phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(3-chlorophenyl)-4,6-bis(tribromomethyl)-1,3,5-triazine and the like.Other triazine type photoacid generators useful in the present inventionare disclosed in U.S. Pat. No. 5,366,846, herein incorporated byreference.

The s-triazine compounds are condensation reaction products of certainmethyl-halomethyl-s-triazines and certain aldehydes or aldehydederivatives. Such s-triazine compounds may be prepared according to theprocedures disclosed in U.S. Pat. No. 3,954,475 and Wakabayashi et al.,Bulletin of the Chemical Society of Japan, 42, 2924-30 (1969).

Onium salts with weakly nucleophilic anions are particularly suitablefor use as photoacid generators in the present invention. Examples ofsuch anions are the halogen complex anions of divalent to heptavalentmetals or non-metals, for example, antimony, tin, iron, bismuth,aluminum, gallium, indium, titanium, zirconium, scandium, chromium,hafnium, copper, boron, phosphorus and arsenic. Examples of suitableonium salts include, but are not limited to: diaryl-diazonium salts andonium salts of group VA and B, IIA and B and I of the Periodic Table,for example, halonium salts, quaternary ammonium, phosphonium andarsonium salts, aromatic sulfonium salts and sulfoxonium salts orselenium salts. Examples of suitable onium are disclosed in U.S. Pat.Nos. 4,442,197; 4,603,101; and 4,624,912, all incorporated herein byreference. The sulfonated esters useful as photoacid generators in thepresent invention include sulfonyloxy ketones. Suitable sulfonatedesters include, but are not limited to: benzoin tosylate, t-butylphenylalpha-(p-toluenesulfonyloxy)-acetate, and t-butylalpha-(p-toluenesulfonyloxy)-acetate. Such sulfonated esters aredisclosed in the Journal of Photopolymer Science and Technology, vol. 4,No. 3,337-340 (1991), incorporated herein by reference.

Suitable halogenated sulfonyloxy dicarboximides useful as photoacidgenerators in the present invention include, but are not limited to:1(((trifluoromethyl)sulfonyl)oxy)-1H-pyrrole-2,5-dione;N-((perfluorooctanesulfonyl)oxy)-5-norbornene-2,3-dicarboximide;1-(((trifluoromethyl)sulfonyl)oxy)-2,5-pyrrolidinedione;3a,4,7,7a-tetrahydro-2-(((trifluoromethyl)sulfonyl)oxy)-4,7-methano-1H-isoindole-1,3(2H)-dione;2-(((trifluoromethyl)sulfonyl)oxy)-1H-benz(f)isoindole-1,3(2H)-dione;3,4-dimethyl-1-(((trifluoromethyl)sulfonyl)oxy)-1H-pyrrole-2,5-dione;2-(((trifluoromethyl)sulfonyl)oxy)-1H-isoindole-1,3(2H)-dione;2-(((trifluoromethyl)sulfonyl)oxy)-1H-benz(de)isoquinoline-1,3(2H)-dione;4,5,6,7-tetrahydro-2-(((trifluoromethyl)sulfonyl)oxy)-1H-isoindole-1,3(2H)-dione;3a,4,7,7a-tetrahydro-2-(((trifluoromethyl)sulfonyl)oxy)-4,7-epoxy-1H-isoindole-1,3(2H)-dione;2,6-bis-(((trifluoromethyl)sulfonyl)oxy)-benzo(1,2-c:4,5-c′)dipyrrole-1,3,5,7(2H,6H)-tetrone;hexahydro-2,6-bis-(((trifluoromethyl)sulfonyl)oxy)-4,9-methano-1H-pyrrolo(4,4-g)isoquinoline-1,3,5,7(2H,3aH,6H)-tetrone;1,8,8-trimethyl-3-(((trifluoromethyl)sulfonyl)oxy)-3-azabicyclo(32.1)octane-2,4-dione;4,7-dihydro-2-(((trifluoromethyl)sulfonyl)oxy)-4,7-epoxy-1H-isoindole-1,3(2H)-dione;3-(1-naphthalenyl)-4-phenyl-1--(((trifluoromethyl)sulfonyl)oxy)-1H-pyrrole-2,5-dione;3,4-diphenyl-1--(((trifluoromethyl)sulfonyl)oxy)-1H-pyrrole-2,5-dione;5,5′-(2,2,2-trifluoro-1-(trifluoromethyl)ethylidene)bis(2-(((trifluoromethyl)sulfonyl)oxy)-1H-isoindole-1,3(2H)-dione;tetrahydro-4-(((trifluoromethyl)sulfonyl)oxy)-2,6-methano-2H-oxireno(f)isoindole-3,5(1aH,4H)-dione;5,5′-oxybis-2-(((trifluoromethyl)sulfonyl)oxy)-1H-isoindole-1,3(2H)-dione;4-methyl-2-(((trifluoromethyl)sulfonyl)oxy)-1H-isoindole-1,3(2H)-dione;3,3,4,4-tetramethyl-1-(((trifluoromethyl)sulfonyl)oxy)-2,5-pyrrolidinedioneand mixtures thereof. It is preferred that the halogenated sulfonyloxydicarboximides comprise one or more of1(((trifluoromethyl)sulfonyl)oxy)-1H-pyrrole-2,5-dione;N-((perfluorooctanesulfonyl)oxy)-5-norbornene-2,3-dicarboximide; and1-(((trifluoromethyl)sulfonyl)oxy)-2,5-pyrrolidinedione, and morepreferablyN-((perfluorooctanesulfonyl)oxy)-5-norbornene-2,3-dicarboximide.

The photoactive components are typically added to photoresistcompositions in an amount sufficient to generate a latent image in acoating layer of resist material upon exposure to activating radiation.When the photoactive component is a photoacid generator, the amount istypically in the range of 0.1 to 10 percent by weight, based on theweight of the resin, and preferably 1 to 8 percent by weight. It will beappreciated by those skilled in that art that more than one photoacidgenerators may be used advantageously in the photoresist compositions ofthe present invention.

Any spirocyclic polymers of the present invention may be advantageouslyused as the resin binders in the photoresist compositions of the presentinvention. It will appreciated by those skilled in the art that morethan one resin binder may be used in the photoresist compositions of thepresent invention, including more than one spirocyclic resin binder.Thus, the spirocyclic resin binders of the present invention may beadvantageously combined with one or more other resin binders.

The optional additives that may be used in the photoresist compositionsof the present invention include, but are not limited to: anti-striationagents, plasticizers, speed enhancers, fillers, dyes and the like. Suchoptional additives will be present in relatively minor concentrations ina photoresist composition except for fillers and dyes which may be usedin relatively large concentrations, e.g. in amounts of from about 5 to30 percent by weight, based on the total weight of the composition's drycomponents.

The photoresist compositions of the present invention may be readilyprepared by those skilled in the art. For example, a photoresistcomposition of the invention can be prepared by dissolving thecomponents of the photoresist in a suitable solvent. Such suitablesolvents include, but are not limited to: ethyl lactate, ethylene glycolmonomethyl ether, ethylene glycol monomethyl ether acetate, propyleneglycol monomethyl ether, propylene glycol monomethyl ether acetate,3-ethoxyethyl propionate, 2-heptanone, γ-butyrolactone, and mixturesthereof. When the resin binder is a spirocyclic lactone polymer, it ispreferred that the solvent comprises γ-butyrolactone, and morepreferably the solvent is a mixture of γ-butyrolactone and 2-heptanone.Thus, it is preferred that photoresist compositions comprisingspirocyclic resin binders including as polymerized units spirocyclicolefin monomers of Formula I, and preferably those of Formulae VII orVIII, contain y-butyrolactone.

Typically, the solids content of the photoresist composition varies fromabout 5 to about 35 percent by weight, based on the total weight of thecomposition. The resin binder and photoacid generators should be presentin amounts sufficient to provide a film coating layer and formation ofgood quality latent and relief images.

Such photoresist compositions may be applied to a substrate by any knownmeans, such as spinning, dipping, roller coating and the like. When thecompositions are applied by spin coating, the solids content of thecoating solution can be adjusted to provide a desired film thicknessbased upon the specific spinning equipment utilized, the viscosity ofthe solution, the speed of the spinner and the amount of time allowedfor spinning.

Photoresist compositions including the spirocyclic polymers of thepresent invention are useful in all applications where photoresists aretypically used. For example, the compositions may be applied oversilicon wafers or silicon wafers coated with silicon dioxide for theproduction of microprocessors and other integrated circuit components.Aluminum-aluminum oxide, gallium arsenide, ceramic, quartz, copper,glass and the like are also suitable employed as substrates for thephotoresist compositions of the invention.

Once the photoresist composition is coated on a substrate surface, it isdried by heating to remove any solvent. It is preferably dried until thecoating is tack free. Thereafter, it is imaged through a mask in aconventional manner. The exposure is sufficient to effectively activatethe photoacid component of the photoresist to produce a patterned imagein the resist coating layer, and more specifically, the exposure energytypically ranges from about 1 to 100 mJ/cm², dependent upon the exposuretool and the components of the photoresist composition.

The photoresist compositions of the present invention are preferablyactivated by a short exposure wavelength, particularly a sub-300 nm,such as UV, and more preferably a sub-200 nm exposure wavelength.Particularly preferred wavelengths include 248, 193, 157 nm and 11-15nm. However, the photoresist compositions of the present invention maybe used at higher wavelengths, such as, but not limited to, visible,e-beam and x-ray. Following exposure, the film layer of the compositionis preferably baked at temperatures ranging from about 70° C. to 160° C.Thereafter, the film is developed. The exposed resist film is renderedpositive working by employing a polar developer, preferably an aqueousbased developer, such as quaternary ammonium hydroxide solutions, suchas tetra-alkyl ammonium hydroxide, preferably a 0.26 Ntetramethylammonium hydroxide; various amine solutions, such asethylamine, n-propylamine, diethylamine, triethylamine or methyldiethylamine; alcohol amines, such as diethanolamine, triethanolamine;cyclic amines, such as pyrrole, pyridine, and the like. One skilled inthe art will appreciate which development procedures should be used fora given system.

After development of the photoresist coating, the developed substratemay be selectively processed on those areas bared of resist, forexample, by chemically etching or plating substrate areas bared ofresist in accordance with procedures known in the art. For themanufacture of microelectronic substrates, e.g. the manufacture ofsilicon dioxide wafers, suitable etchants include, but are not limitedto, a gas etchant, such as a chlorine- or fluorine-based etchant, suchas Cl₂ or CF₄/CHF₃ etchant applied as a plasma stream. After suchprocessing, the resist may be removed from the processed substrate usingany stripping procedures known in the art.

The following examples are intended to illustrate further variousaspects of the present invention, but are not intended to limit thescope of the invention in any aspect.

EXAMPLE 1

Norbornene butyrolactone (or4′,5′-dihydro-(1a,2a,4a)-spiro[bicyclo[2.2.1]hept-5-ene-2,3′(2′H)-furan]-2′-one)was prepared as follows. Methylene butyrolactone was dissolved indichloromethane and freshly cracked cyclopentadiene was added. Thereaction mixture was stirred at room temperature for 3 hours, heated to40° C. and held at 40° C. overnight. The reaction mixture was thenslowly cooled to room temperature. The methylene chloride was removedunder reduced pressure, leaving an oil. The crude oil was then distilledunder reduced pressure to afford pure product.

EXAMPLE 2

Norbornene valerolactone was prepared as follows. A solution ofvalerolactone (50.1 g) in 150 mL of anhydrous THF was placed in athree-neck-bottomed flask at −78° C. (dry ice/acetone bath). To it,solution of lithium dimethylamine (“LDA”) (250 mL, 2M) in 250 mLanhydrous THF was added dropwise. The reaction mixture was stirred atthis temperature for 4 hours. Then, the thermal cracking ofparaformaldehyde (36.94 g, excess) was bubbled into the reactionmixture. After the paraformaldehyde was all cracked, the reactionmixture was stirred overnight and allowed to gradually warm to roomtemperature. Then, the solvent was removed by rotary pump and theresidue was added 500 mL dichloromethane and washed with NaHCO₃ (aq,sat.) and water several times (3×500 mL). The organic solvent was driedover MgSO₄ and then removed by rotary pump. The desired product,methylene-valerolactone, was distilled under vacuum (135-140° C./8 mmHg).

The methylene-valerolactone was then dissolved in dichloromethane andfreshly cracked cyclopentadiene was added. The reaction mixture wasstirred at room temperature for 3 hours, then heated to 40° C., and heldat 40° C. overnight. The reaction mixture was then slowly cooled to roomtemperature. The dichloromethane was removed under reduced pressure,leaving an oil. The crude oil was then distilled under reduced pressureto afford pure product.

EXAMPLE 3

To a 50 ml glass vial equipped with a Teflon coated stir bar is added2.64 g (13.6 mmol) of 5-norbornenecarboxylic acid tert-butyl ester,0.952 g (5.34 mmol) ofspiro[bicyclo[2.2.1]hept-5-ene-2,3′(2′H)-furan]-2′,5′(4′H)-dione, asshown by the following formula

together with 50 mil of freshly distilled dichloroethane. The solutionis degassed under an argon atmosphere. A 10 ml glass vial equipped witha Teflon coated stir bar is then charged with 0.0365 g (0.1 mmol) ofh³-allylpalladium chloride dimer and 2 ml of dichloroethane. Another 10ml glass vial is charged with 0.0195 g (0.1 mmol) of silvertetrafluoroborate and 2 ml of dichloroethane. The catalyst solution isthen prepared by mixing the allylpalladium chloride dimer solution withsilver tetrafluoroborate solution inside a dry box. Silver chloride saltwill immediately precipitate, which is then filtered, and a clear yellowsolution is obtained. This active yellow catalyst solution is added tothe monomer solution via a syringe and the reaction mixture is allowedto stir for 20 hours at 60° C. Solids that form typically precipitate inthe solution. The solution is cooled, concentrated in arotary-evaporator, and precipitated into hexane to obtain the polymer.

EXAMPLE 4

The polymer from Example 3 (1.4 g) is placed in a bottle, together with0.0895 g of triphenyl sulfonium trifluoromethane sulfonate(TPS-Triflate), 0.00165 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),6.11 g of methyl amyl ketone and 3.05 g of propylene glycol methyl etheracetate. The mixture is then stirred on a rolling mill until all solidscompletely dissolve. The solution is then filtered through a 0.05 mmporous filter into a clean bottle. The resulting resist is spun on asilicon wafer, baked on a hot plate at 135° C. for 60 sec, exposed on anISI 193 nm step-and-repeat printer, post-exposure baked at 155° C. for60 sec and then developed in an aqueous solution of 2.38%tetramethylammonium hydroxide. Typically, adhesion is improved andlittle or no swelling of the resist features is observed.

EXAMPLE 5

To a 50 ml glass vial equipped with a Teflon coated stir bar is added1.943 g (10.0 mmol) of TBN-CA, 1.64 g (10.0 mmol) of4′,5′-dihydro-(1a,2a,4a)-spiro[bicyclo[2.2.1]hept-5-ene-2,3′(2′H)-furan]-2′-one,as shown by the following formula

together with 50 ml of freshly distilled dichloroethane. The solution isdegassed under an argon atmosphere. A 10 ml glass vial is equipped witha Teflon coated stir bar and then is charged with 0.0365 g (0.1 mmol) ofη³-allylpalladium chloride dimer and 2 mL of dichloroethane. Intoanother 10 mL glass vial is charged with 0.0195 g (0.1 mmol) of silvertetrafluoroborate and 2 mL of dichloroethane. The catalyst solution isprepared by mixing the allylpalladium chloride dimer solution withsilver tetrafluoroborate solution inside a dry box. Silver chlorideimmediately precipitates, and the mixture is then filtered, to obtain aclear yellow solution. This active yellow catalyst solution is added tothe monomer solution via a syringe and the reaction mixture is thenallowed to stir for 20 hours at 60° C. Solids that form typicallyprecipitate in the solution. The solution is cooled, concentrated in arotary-evaporator, and precipitated into hexane to obtain the polymer.

EXAMPLE 6

The procedure of Example 4 is repeated except that 1.4 g of the polymerfrom Example 5 is used and the solvent consists of 4.58 gg-butyrolactone and 4.58 g 2-heptanone. Typically, adhesion is improvedand little or no swelling of the resist features is observed.

EXAMPLE 7-22

Polymers useful as photoresist binders are shown in the following Table.Such polymers are prepared according to the procedures described inExamples 3 or 5, as noted in the Table.

TABLE Monomer 1 Monomer 2 Monomer 3 Polymer Example Mol % Mol % Mol %Preparation  7

Example 5  8

Example 5  9

Example 5 10

— Example 3 11

— Example 3 12

—

Example 3 13

—

Example 3 14

Example 5 15

— Example 5 16

— Example 5 17

— Example 5 18

Example 5 19

Example 5 20

Example 5 21

Example 5 22

Example 5

EXAMPLE 23

The following polymer was prepared.

A mixture of ethyltricyclodecane carboxylate (15.16 g), maleic anhydride(6.60 g), norbornene-spiro-butylactone (2.80 g), and dimethyl2,2′-azobis(2-methylpropionate) (0.31 g, 1 mole % total monomers) in12.28 g ethyl acetate was placed in a round-bottomed flask. Afterstirring for 5 minutes (until all solids were dissolved), the flask wasput into a pre-heated 70° C. oil bath. The reaction mixture was stirredat this temperature for 24 hours. After cooling, 25.0 g oftetrahydrofuran was added. The polymer was isolated by precipitationinto 1.5 L of hexane/isopropanol (1/1, w/w.). The resulting suspensionwas stirred for 120 minutes. The polymer was filtered off and washedwith an additional 200 mL of hexane. The polymer was dried in a vacuumoven at 40° C. overnight. The overall yield was 25%.

EXAMPLE 24

The polymer norborene/(spiro-2-2-α-butyrolactone)-5-norborene/norborneneethyl tricyclodecane carboxylate/maleic anhydride (7.5/7.5/35/50 mol %)was prepared.

Into a 100 mL round bottom flask were added norbornene 1.22 g (0.013mol), (spiro-2-2-α-butyrolactone)-5-norborene 2.13 g (0.013 mol), maleicanhydride 8.86 g (0.086 mol), norbornene ethyl tricyclodecanecarboxylate 18.18 grams (0.060 moles), dimethyl2,2′-azobis(2-methylpropionate) 0.4 g (0.0017 mol) and 15 g ethylacetate. A magnetic stir bar was added to the flask and the solution wasstirred for approximately 15 minutes to dissolve the solids. Once allthe solids were dissolved, the flask was placed in a hot oil bath thatwas preheated to 80° C. A condenser and nitrogen line were attached ontop and the reaction was allowed to stir for 24 hours. After 24 hoursthe heat was removed and the flask was allowed to cool to roomtemperature. After cooling, the contents of the flask was precipitatedinto 1.5 L of hexanes/isopropanol (50/50 w/w). The precipitated solutionwas stirred for 1.5 hours and then the polymer was isolated via a glassfritted funnel. The polymer was then dried for 4 hours in a hood andthen overnight in a vacuum oven at room temperature. This reactionyielded 15 grams of polymer (50%).

EXAMPLE 25

Photoresists containing the polymers of Examples 7 to 22 are prepared byaccording to Examples 4 or 6, except that the polymers are taken up inγ-butyrolactone.

What is claimed is:
 1. A polymer comprising as polymerized units one ormore spirocyclic olefin monomers of the formula

wherein A=O, S, and NR¹; R¹=phenyl, substituted phenyl, benzyl,substituted benzyl, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; G=C(Z′),O, S, and NR²; R²=H, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; E and Ware independently selected from C(Z′), O, NR₂ and a chemical bond; Z′=Oor S; m=0 to 2; m′=0 to 2; 1=0 to 5; and p=0 to 5; n=1; provided thatl+p=3 to 5 wherein T and L are taken together and selected from thegroup consisting of a double bond and a 5 to 8-membered unsaturatedring.
 2. The polymer of claim 1 wherein the spirocyclic olefin monomerhas a formula:

wherein A, E, W, G, l, m, n, and p are as defined in claim
 1. 3. Thepolymer of claim 1 wherein the spirocyclic olefin monomer has theformula:

wherein A, E, W, G, l, m, n, and p are as defined in claim
 1. 4. Amethod of polymerizing one or more spirocyclic olefinic monomers to forma polymer comprising as polymerized units one or more spirocyclic olefinmonomers, comprising the step of contacting the one or more spirocyclicolefinic monomers with one or more catalysts selected from the groupconsisting of palladium(II) polymerization catalyst, nickel(II)polymerization catalyst and free radical polymerization catalyst;wherein the spirocyclic olefin monomers has the formula

wherein A=O, S, and NR¹; R¹ phenyl, substituted phenyl, benzyl,substituted benzyl, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; C=C(Z′),O, S, and NR²; R²=H, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; E and Ware independently selected from C(Z′), O, NR² and a chemical bond; Z′=Oor S; m=0 to 2; m′=0 to 2; l=0 to 5; and p=0 to 5; n=1; provided thatl+p=3 to 5 wherein T and L are taken together and selected from thegroup consisting of a double bond and a 5 to 8-membered unsaturatedring.
 5. The method of claim 4 wherein the palladium(II) catalystcomprises palladium dihalide, nonionic palladium(II)-halide complexes,(Pd(RCN)₄)(BF₄)₂, where R is (C₁-C₄)alkyl, palladium(II)-alkylcomplexes, and (η³-allyl)palladium(II) compounds with weaklycoordinating counterions.
 6. The method of claim 4 wherein thepalladium(II) catalyst comprises (Pd(RCN)₄)(BF₄)₂, where R is(C₁-C₄)alkyl, (η³-allyl)palladium(II) compounds with weakly coordinatingcounterions, and mixtures thereof.
 7. The method of claim 4 wherein thefree radical polymerization catalyst is selected from the groupconsisting of hydrogen peroxide, tert-butyl hydroperoxide, sodiumpersulfate, potassium persulfate and lithium persulfate.
 8. The methodof claim 4 wherein the nickel(II) polymerization catalyst is selectedfrom the group consisting of nickel(II) catalysts having as ligands atleast one of salicylaldimine or substituted salicylaldimine and at leastone of acetonitrile or phosphine.
 9. A photoresist compositioncomprising a resin binder and a photoactive component, wherein the resinbinder comprises a spirocyclic polymer comprising as polymerized unitsone or more spirocyclic olefin monomers of the formula

wherein A=O, S, and NR¹; R¹=phenyl, substituted phenyl, benzyl,substituted benzyl, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl G=C(Z′),O, S, and NR²; R²=H, (C₁-C₈)alkyl and substituted (C₁-C₈)alkyl; E and Ware independently selected from C(Z′), O, NR² and a chemical bond; Z′=Oor S; m=0 to 2; m′=0 to 2; l=0 to 5; and p=0 to 5; n=1; provided thatl+p=3 to 5 wherein T and L are taken together and selected from a groupconsisting of a double bond and a 5 to 8-membered unsaturated dog. 10.The photoresist composition of claim 9 further comprising a solvent. 11.The photoresist composition of claim 10 wherein the solvent comprisesethyl lactate, ethylene glycol monomethyl ether, ethylene glycolmonomethyl ether acetate, propylene glycol monomethyl ether, propyleneglycol monomethyl ether acetate, 3-ethoxyethyl propionate, 2-heptanone,γ-butyrolactone, and mixtures thereof.
 12. The photoresist compositionof claim 11 wherein the solvent is selected from γ-butyrolactone ormixtures of γ-butyrolactone and 2-heptanone.
 13. A method for forming aphotoresist relief image, including the steps of applying a coatinglayer of the photoresist composition of claim 9; exposing thephotoresist coating layer to patterned activating radiation; developingthe exposed photoresist coating layer to provide a photoresist reliefimage.
 14. A polymer comprising as polymerized units one or morespirocyclic olefin monomers and one or more cyclic olefin monomers;wherein the spirocyclic olefin monomers are bound to the polymerbackbone through the olefinic carbons and wherein the spirocyclic olefinmonomer comprises one or more electron withdrawing groups within atleast one of the spirocyclic rings; wherein the electron withdrawinggroups are selected from the group consisting of thiolactones,thioimides, lactams, and thiolactames.
 15. The polymer of claim 14wherein the cyclic olefin monomer is a (C₅-C₁₀) cyclic olefin monomer.16. The polymer of claim 14 wherein the cyclic olefin monomer has anacid cleavable group.
 17. A polymer comprising as polymerized units oneor more spirocyclic olefin monomers wherein the spirocyclic olefinmonomers are bound to the polymer through the olefin carbons and whereinthe spirocyclic olefin monomer has the formula

wherein A=CH₂; G=C(Z′), S, and NR²; R²=H, (C₁-C₈)alkyl and substituted(C₁-C₈)alkyl; E and W are independently selected from C(Z′), O, NR² anda chemical bond; Z′=S; m=0 to 2; m′=0 to 2; n=1; l=0 to 5; and p=0 to 5;provided l+p=3 to 5 and provided that at least one of E, W and G isC(Z′), wherein T and L are taken together and selected from the groupconsisting of a double bond and a 5 to 8-membered unsaturated ring. 18.A polymer comprising as polymerized units one or more spirocyclic olefinmonomers selected form the monomers of Formulae II and III

wherein Z=CH₂, C(S), O or S; X and Y are independently selected fromCH₂, C(S), O or NR²; and R²=H, (C₁-C₈)alkyl and substituted(C₁-C₈)alkyl; provided that at least one of X, Y and Z is C(S); andwherein the spirocyclic monomer is optionally substituted.